Synthetic analogues of the microporous minerals umbite (AM-2) and penkvilksite, polytype 2O (AM-3), have been prepared. The facile syntheses of two other titanosilicates, AM-1 and AM-4, have also been reported. AM-1 and the previously reported, layered titanosilicate known as JDF-L1 have been shown to have the same structure. AM-4 is a new microporous titanosilicate with a unique and unknown structure, containing eight different Na sites. All AM-n materials have been characterized by several techniques, viz. SEM, powder XRD, single- and triple-quantum 23Na and 29Si MAS NMR, water adsorption measurements, and TGA/DSC. AM-n materials are thermally stable up to ca. 600 °C. The dehydration−hydration processes seem to be reversible (or quasi reversible) for AM-1, -2, and -3 but not so for AM-4.

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The control of quantum correlations in solid state systems by means of material engineering is a broad avenue to be explored, since it makes possible steps toward the limits of quantum mechanics and the design of novel materials with applications on emerging quantum technologies. In this context, this Letter explores the potential of molecular magnets to be prototypes of materials for quantum information technology. More precisely, we engineered a material and from its geometric quantum discord we found significant quantum correlations up to 9540 K (even without entanglement); and, in addition, a pure singlet state occupied up to around 80 K (above liquid nitrogen temperature). These results could only be achieved due to the carboxylate group promoting a metal-to-metal huge magnetic interaction. Keywords: Quantum discord, Geometric correlations, Molecular magnetsQuantum entanglement has received a considerable attention as a remarkable resource for quantum information processing [1][2][3]. In spite of that, it is fragile and can easily vanish due to the inevitable interaction of the system with its environment [4]; and due to this condition, it was thought that entanglement could only exist at low temperatures. However, recently, it has been shown that entanglement can also exist at higher temperatures, and can be detected through the measurement of some thermodynamic observables [5][6][7][8][9][10][11][12][13][14][15][16][17].Nevertheless, quantum entanglement does not encompass all quantum correlations in a system and recent studies have greatly expanded the notion of quantum correlations [18][19][20][21][22][23][24][25][26][27][28][29]; and the measure of quantum excess of correlations has been named as quantum discord [19][20][21]. In the last years, it was understood that quantum discord has an important role in many quantum information processing even without entanglement. Notably, this quantity can also detect quantum phase transitions [25,30,31].Despite much effort by the scientific community, there are only a few results on the analytical expression of quantum discord; and only for a certain class of states an exact solution is known [23-27, 32, 33]. This fact stimulated alternative measurements of quantum discord, theoretically and experimentally [22,24,29,[34][35][36]. The recent demonstration that quantum discord can be measured by the thermodynamic properties of solids, such as magnetic susceptibility, internal energy [35][36][37], specific heat [35,36] and even neutron scattering data [22], shows that quantum correlations can be related to significant macroscopic effects allowing the measurement and the control of quantum correlations in solid state systems by means of material engineering. Thus, the design of novel materials becomes an actual challenge to overcome.In this direction, molecular magnets can be an excellent opportunity to achieve this goal as prototypes of materials for quantum information technology. They combine classical properties, found in any macroscopic magnet, with quantum one...

The new redox-noninnocent azoaromatic pincers 2-(arylazo)-1,10-phenanthroline (L) and 2,9-bis(phenyldiazo)-1,10-phenanthroline (L) are reported. The ligand L is a tridentate pincer having NNN donor atoms, whereas L is tetradentate having two azo-N donors and two N-donor atoms from the 1,10-phenanthroline moiety. Reaction of FeCl with L or L produced the pentacoordinated mixed-ligand Fe(II) complexes FeLCl (1) and FeLCl (2), respectively. Homoleptic octahedral Fe(II) complexes, mer-[Fe(L)](ClO) [3](ClO) and mer-[Fe(L)](ClO) [4](ClO), have been synthesized from the reaction of hydrated Fe(ClO) and L or L. The ligand L, although having four donor sites available for coordination, binds the iron center in a tridentate fashion with one uncoordinated pendant azo function. Molecular and electronic structures of the isolated complexes have been scrutinized thoroughly by various spectroscopic techniques, single-crystal X-ray crystallography, and density functional theory. Beyond mere characterization, complexes 1 and 2 were successfully used as catalysts for the aerobic oxidation of primary and secondary benzylic alcohols. A wide variety of substituted benzyl alcohols were found to be converted to the corresponding carbonyl compounds in high yields, catalyzed by complex 1. Several control reactions were carried out to understand the mechanism of this alcohol oxidation reactions.

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